Surface active polyethylene and polypropylene imine nu-aryl carbamates



2,839,568 Patented June 17, 1.958

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SURFACE ACTIVE POLYETHYLENE AND POLY- PROPYLENE IMENE N-ARYL CARBAMATESHerman S. Bloch, Chicago, 111., and Donald R. Strehlau, Drexel Hill,Pa., assignors to Universal Oil Products Company, Chicago, IiL, acorporation of Delaware No Drawing. Application June 29, 1954 Serial No.440,257

1 Claim. (Cl. 260-472) This application is a continuation-in-part of ourcopending application Serial No. 182,402, filed August 30, 1950, nowabandoned.

This invention relates to a process for the manufacture of certainderivatives of alkylaryl isocyanates and to novel compositions of mattercontaining these products, individual members of this class of productspossessing surface activity as well as other useful properties. Thealkylaryl isocyanate derivatives of the present invention areparticularly useful as detergents, either individually or in admixturewith other substantially neutral organic compounds having surface activeproperties or which enhance the surface activity of the detergentcompound.

In accordance with well-established principles concerning the phenomenonof detergency exhibited by certain compounds in aqueous as well asessentially organic solvent solutions, the selection of a suitablecompound which will possess surface activity depends upon the choice ofthe proper chemical groups which when integrated into a composition ofwell-defined structure and composition will impart a critical balance ofhydrophilic and hydrophobic groups in the molecular structure of theresulting compound such that when the latter is dissolved in a suitablesolvent, individual molecules of the compound will become oriented insolution with other molecules of the compound to form detergentmicelles. In general, the essential structure of compounds which exhibitsurface activity or detergency in solution have on one end of themolecule a hydrocarbon group containing a sufiicient number of carbonatoms to exert a hydrophobic efiect in solution and on the other end aradical having a sufficient I number of water-solubilizing groups toexert a hydrophilic effect of sufiicient magnitude to substantiallybalance the eflect of the hydrophobic group in solution. Hydrophobicgroups heretofore found suitable for incorporation into surface'activecompounds include the long chain aliphatic radicals generally containingfrom to about 20 carbon atoms and the alkyl-substituted aryl hydrocarbongroups of both the monoand polycyclic aryl series, the alkyl substituentfor themonocyclic series containing at least 8, up to about 20 carbonatoms per group and for the polycyclic aryl series at least 3, up toabout 9 carbon atoms per group. Of the hydrophilic radicals, the carboxyor carboxylate group as represented by the ordinary soaps, the sulfoorsulfonate group as represented by the alkylaryl sulfonates, and thepolyoxyalkylene groups as represented by the poly-ethylene glycolalkylphenylates are some of the hydrophilic radicals present indetergent products heretofore provided. The present invention isdirected to surface active compounds of non-ionic or slightly cationicproperties which may be structurally considered as alkylarylhydrocarbons of the monoand bicyclic series joined through a urethanelinkage to a poiyalkylenepolyamino chain as the hydrophilic portion ofthe molecule, both the hydrophilic and hydrophobic radicals of which arecritical to the development of surface activity in the resultingcompounds. The present products are further characterized as having analkylaryl group in which the alkyl substituent contains at least 3, upto about 9 carbon atoms in the case of the polycyclic aryl derivativesand at least 8, up to about 20 carbon atoms per alkyl group when thearyl group is monocyclic in character. The hydrophilic group may also bemore explicitly characterized as a vpolyalkylene polyamino substitutedurethane radical, said polyalkylene polyamine chain containing at least5, up to about alkyleneamino units per group.

The present surface active compounds uniformly correspond to thefollowing general structure:

[(R1O)-(RNH).H| products of the above structure being formed by thecondensation of an alkylaryl isocyanate with an alkanol amine, followedby condensing the reaction product with an alkylene imine to introducethe hydrophilic poly- (alklyeneamino) chain into the molecularstructure. In the above general formula, X is a urethano group havingthe structure corresponding to the formula:

wherein R is the long chain alkyl substituent on 'the'aryl nucleus, Ar,containing from 8 to about 20 carbon atoms when Ar is monocyclic andfrom 3 toabout 9 when is bicyclic, R is a short chain alkyl groupcontaining from 1 to 2 carbon atoms, n is a number selected from O, 1,and 2, R and R are alkylene groups containing from 2 to 5 carbon atoms,a is selected from 1 and '2, b and c are selected from O, 1, and 2, b+cbeing at least 1, a+b being a whole number less than 4 and Z is anelectronegative radical of an acid which may or may not be associatedwith the amino nitrogen atoms of the poly-(alkyleneamino) chain, asindicated by the subscript t which may be 0 or a finite whole number; Inorder for the resulting product to have surface activity, the totalnumber of alkyleneamino units in each hydrophilic chain, that is, thevalue of each s, must be at least 5 and is preferably not more thanabout 150, depending upon the size of the hydrophobic hydrocarbon groupand the value of subscript a in the above formula. The

water-solubilizing poly-alkylenepolyamino chain in the structure of theproduct may be formed in situ by re-' acting the urethane intermediatewith the alkylene imine monomer, or may be formed by aninter-condensation reaction of the alkylaryl urethane with an alkyleneimine polymer containing the desired number ofalkylene imine units, thepolymer being formed in a reaction preceding the condensation with theurethane intermediate.

One object of this invention is to provide a novel class of organiccompounds utilizable as surface active agents neutral anionic, ionic ornon-ionic detergents. Another object of this invention is to providedetergents insolid form which possess the wax-like consistency and otherphysical properties of soap and are capable of latheringto formmucilaginous dispersions of the detergent in a solvent, but which, onthe other hand, unlike soap, do

' not precipitate insoluble calcium or magnesium curd when dissolved inhard water containing calcium or magnesium ions in solution. A furtherobject of this invention is to prepare a substantially non-ionic or onlyslightly cationic surface-active agent soluble in water and compatiblewith other cationic; anionic or non-ionic surface active agents.

In one of its embodiments this invention relates to essentially organiccompounds having the following general formula:

Ila-(+11) [X]-,-N-[(RQNH),H].

1 -lb in which Formula X, is a urethano group having, the structurecorresponding to the formula:

wherein Ar is a poly-substituted aryl hydrocarbon group selected fromthe mono and bicyclic aromatic hydrocarbons, R is an allgyl groupcontaining from 8 to about 20 carbon atoms when Ar is monoc'yclic andfrom 3 to about 9 carbon atoms when AI is bicyclic, R is an alkylgroupcontaining from 1 to l carbon atoms, :2 is a whole number selectedfrom O, l, and 2, R and R are independentlyselected from alkylenecontaining from 2 to 5 carbon atoms, s. is a whole number selected from5 to about 1 50,- ais selected from 1 and 2, and b and c are selectedfrom 0, 1, and 2, b+c being at least 1, a+b+c being a wholenumber lessthan 4, Z is an acid-derived anion and t is selected from 0, l, and awhole number having a value selected'from 1 to l+s(b+c).

Another embodiment of the invention is directed to a process for.preparing a surface active agent which comprises reacting analkylarylamine having a single aryl substituent on thearyl nucleuscontaining from 8 to about. carbon. atoms when the aryl group ismonocyclic and from 3 to 9 carbon atoms when the aryl nucleus isbicyclic with carbonyl chloride, thereafter reacting the resultingN-alkylarylisocyanate with an alkanolamine selected from, the. mono-,di-, and trialkanolamines containing from 2 to- Scarbon atoms peralkanol group and condensing the resulting product with .a compoundselected from thegroup'consisting of an alkylene imine and apolyalkylenepolyamine in which the alkylene group contains from'2 toabout-5' carbon atoms and continuing the reaction until the condensationproduct contains from about 5 to about 150 alkylene amino units permolecule.

As heretofore indicated, the size of or the number of carbon atoms inthe hydrophobic alkylaryl portion of thepresent product and the numberof alkyleneamino units in the polyalkylenepolyamino radical constitutingthe-hydrophilic chain substituted on the aryl nucleus must be maintainedwithin defined limitations in order for the resulting product to possesssurface active properties, particularly the property of detergency inaqueous or non-aqueous solvents. In general, the size of the hydrophobicand-hydrophilic groups must be within certain defined limits to providea product in which the hydrophobic group substantially balances theeffect of the hydrophilic group in solution, such critical sizerelationship being apparently essential to the formation of the micellestructure when the product is dissolved in a solvent.

In the usual and preferred process of producing the present surfaceactive products the starting material is the alkylaryl hydrocarbon whichconstitutesthe hydrophobic portion of the product molecule on which theisocyanate radical" is subsequently introduced, followed by thestep-wise condensation of'the resulting alkylaryl isocyanate which analkanol amine to provide an intermediate product containing an activehydrogen atom residing in either a terminal hydroxyl group or a primaryor secondary amino group, in: either. of which the amino or hydroxylhydrogen atom is present which is capable of subsequently reacting bycondensation with an alkylene imine or with a polyalkylene polyamine toform a hydrophilic polyalkylenepolyamino chain. Although the inventionis particularly directed to the. monocyclic alkylaryl derivatives hereinprovided, in which the alkyl group contains from 8 to about 20 carbonatoms, certain aIkyI-substitutecl derivatives of the bicyclic arylhydrocarbons of the naphthalene and biphenyl series also provideefiective hydrophobic groups from which the present detergent productsmay be synthesized. In the bicyclic aryl hydrocarbon series, the nuclearialkyl substituent contains at least 3 and preferably not more thanabout 9 carbon atoms in order to provide a hydrophobic alkylarylhydrocarbon group of the proper degree of hydrophobic effectiveness toyield detergent compounds when integrated with the hydrophilic radicalof the present composition. Some of the preferred hydrocarbon startingmaterials of the present process aretthe alkylaryl hydrocarbons formedby alkylation of the aromatic ring with propylene polymers, particularlythe dimers, trimers, tetramers, and pentamers, although alkylates formedby condensation of the. aromatic hydrocarbon starting material with,chlorinated paraifins, alcohols, etc. are also, utilizable asthe startingmaterials. Typical of the; propylene polymer alkylates utilizableherein, as the initialstartingmaterial in the completesynthesis of, thepresent products are such. hydrocarbons as: nonlybenzene,dodecylbenzene, pentadecylbenzene. and octadecylbenzene, thecorresponding ortho-, meta-, and para-,, nonyl-dodecyb, and penta--decyl toluenes, xylenes;. ethylbenzenes, and ethyltoluenes of themono-nuclear aromatic series, hexylnaphthalenes, nonylnaphthalenes,hexylphenylbenzenes, as well as the alkylates formedv from shorter chainolefins such as diisopropylnaphthalene, butylnaphthalene,isobutylnaphthalene, t-butylnaphthalene, amylnaphthalene,octylnaphthalene, amylmethylnaphthalene, isopropylphenylbenzene,p,p-diisopropylphenylbenzene, t-butyl-dimethylphenylbenzene and othersofthe bicyclic aryl hydrocarbon series. The surface active productsprepared from the monocyclic or benzenoid series of. aromatichydrocarbons are particularly preferred as general detergents andemulsifying agents for aqueous systems'because' of their more desirablephysical properties which enable these compounds to beutilizedfor agreater variety of effective detergent purposes than the correspondingalkyl bicyclic aryl derivatives which are generally less soluble inwater and are of higher melting point than the alkylbenzene derivatives.The alkylaryl hydrocarbon starting materials are formed by thewell-known, alkylation process of the art, preferably being formed bythe alkylation of the aryl hydrocarbon with an olefinic hydrocarbonalkylating agent in the presence of antacid-type catalyst at reactionconditions which promote the formation of the mono-substituted longchain alkylaryl hydrocarbon,

When the synthesis of the present surface active products is initiatedwith the alkylaryl hydrocarbon starting material, a procedure which isgenerally applicable to the monoor bicyclic valltylaryl hydrocarbons for.the production of the present surface active products comprises thefollowing series of, successive reaction steps: (1) subjecting the longchain alkyl-substituted aryl hydrocarbon to nitration under reactionconditions which yield a mono nitrated product in which the nitro groupis substituted on one of the nuclear aryl positions, (2) selectivelyreducing the nitro group of the resulting nitro alkylaryl hydrocarbon byhydrogen reduction to form the corresponding amino-substituted alkylarylcompound, (3) re acting the alkylarylamine with phosgene (carbonylchloride) to form the corresponding alkylaryl isocyanate which has thefollowing empirical structure:

(R') .r-NCO (4) thereafter reacting the isocyanate intermediate with analkanol amine selected from the mono-, di-, and trialkanolamineshavingfrom 2 to 5 carbon atoms in their alkanol groups under reactionconditions, such that upon.

completion of the resulting condensation reaction the reaction of thealkylene imine reactant'with the interme-, diate product to form thelong' chain polyalkylenepolyamino radical containing from to about 150alkyleneamino units per chain. The product resulting from the aboveseries of reactions, which is the product of this invention correspondsin its general structure .to the formula heretofore described.

In the synthesis of the present products starting from the alkylarylhydrocarbon, the nitration of the aromatic ring may be effected by anyof the commonly known methods of nitration which yield themono-substituted nitro product, normally effected by reacting thealkylaryl hydrocarbon with concentrated nitric acid, usually in thepresence of a dehydrating agent such as concentrated sulfuric acid. Theselective reduction of the nitro group of the resulting mononitratedproduct is also effected by well-known means, such as reduction withhydrogen generated by zinc and hydrochloric acid, iron an hydrochloricacid, or by catalytic reduction, effected, for example, by passing'themononitroalkyl-aromatic hydrocarbon in the presence of hydrogen over asupported nickel, cobalt, or platinum catalyst, among others for thispurpose. The conversion of the alkylarylmonoamine to the correspondingisocyanate intermediate may, also be accomplished in accordance withwell-known procedures therefor, for example, by reaction of the aminewith carbonyl chloride (also referred to as phosgene) at temperaturessuflicient to maintain the reactants in substantially liquid phase andto effect the carbonylation of the amino group. Although the preferredmethod of forming the isocyanate comprises the aforemerk tionednitration, reduction and reaction or the amine with carbonyl chloride,other methods for converting the alkyl aromatic hydrocarbon to themono-isocyanate derivative may be used.

The treatment of the alkylaryl isocyanate-intermediate to form the finalsurface active product of this invention depends upon the productdesired from the present process and particularly upon the use to bemade of the product. In the reaction of the present alkylaryl'isocyanatewith an alkanol amine to form theintermediate product referred to hereinthe reaction is believed to result primarily in the formation of aurethane linkage involving the condensation of the isocyanate radicalwith the hydroxyl group of the alkanol amine; that is, the one or morehydroxyl groups of the monoor polyalkanolamine are believed to be morereactive in the condensation reaction with the isocyanate than the aminogroup thereof, although the intermediate maynotnecessarily consistexclusively of urethane linkages. The general formula which is believedto represent a major propor tion of the intermediate product of thisinvention prior to condensation with the alkylene imine orpolyalkylenepolyamine reactant is as follows:

condensation reaction with the alkylaryl isocyanate pr'oduces anintermediate believed to consist -primarily'ofia urethane product inwhichthe subscript a of the above formula has a value 1 and b is 0, theintermediate prod ucthavin'g the following structure: a i

the product containing a, terminal primary amino group condensable withthe alkylene imine or polyalkylene polyamine reactant herein provided to,form a hydrophilic radicalcontaining one or, two polyalkylenepolyaminochains per molecule. In the condensation of a" dialkanolaminewith thealkylaryl isocyanate to games presentintermediate product, thejreacti'onmay involve one or two molecules of the isocyanate per moleculeofdialkanolamine,ifsufiicient isocyanate is available in the reactionmixture, 'to forman intermediate product containing one or twohydrophobic alkylaryl groups attached by urethane linkages to thehydroxyl groups of the dialkanolamine as shown in the followingempirical formula representing the structure of the intermediate:

the value of a in the above general formula being 1 or 2. l and b being1 or 0. The diurethane intermediate prod- I uct is-believed to be formedas a principal product when p at least two moles of the alkylarylisocyanate are charged to the condensation reaction per mole ofdialkanolamine and when less than two moles of the former reactant areutilized per mole of isocyanateftheintermediate product is believed tobe a mixtureof products having mono and diurethano linkages; Ifequimolar. ratios of the reactants or a molar excess of alkanolimine areutilized in the intermediate condensation, the product is believedtoconsist primarily of monc-urethanes. .In each instanc'e, however, theresultingintermediate products contain terminal secondary amino radicalscondensable in the subsequent this invention.

erally possess surface activity but are'not highly efiec rive detergentproducts. The condensation of the alkylarylisocyanate reactant with atrialkanolamine reactant to form the intermediate productisalsobelierved to con- 3 tain at least one urethane linkage, dependingupon the molar ratio of isocyanate to alkanolamine reactants charged tothe intermediate condensation reaction. Al-

though trialkanolamines contain three hydroxylgroups; per molecule eachof which may theoretically undergo j condensation with a molecule of'the isocyanate, the presence of the relatively large alkylaryl radicalon the isocyanate reactantlimitsvia steric hindrance thenumber ofisocyanate units may possibly react with the trialkanolamine to notgreater than two, and an intermedi ate product of the followingstructure is believed to be formed: I 9

. in which a is one or two, the resultingintermediate prodnot containingone or two terminal hydroxyl groups, the

active hydrogen atoms of which are capable of under-'.

going condensation with the alkylene imine or poly'alkylenepolyaminereactant in the final stageof, the present synthesis toform thehydrophilic polyalkylenepolyamino chains. In the latter reaction sterichindrance does not apparently limit or control the reactivity of theessenj tially aliphatic alkylene imine with the terminal hy-f droxylgroup, such that .upon contacting the intermediate alkylarylisocyanate-trialkanolamine reaction product with the alkylene imine oralkylene imine polymer in the final stage of the present processatp'ondensaticnrer.

asses-"es action conditions, the reaction proceeds to finality,accompanied by the introduction of the hydrophilicpolyalkylencpolya'rnino radical into the structure of' the product.

, Suitable alkanolamines utilizable in the intermediate reaction includesuch compounds containing from 2 to 5 carbon atoms in the alkanolresidue of this reactant, including the mono-, diand trialkanolamines,such as aminoethanol, V diethanolarninc, tricthanolamine, aminopropanol,dipropanolamine, isopropanolarnine, one or more of'the aminobutanols oran aminopentanoi isomer in whieh the hydroxyl group m'ayoccupy variouspositions on the alkylene chain thereof relative to the amino group. Thecondensation of; the alkylaryl isocyanate with the alkanolamine occursgenerally at temperatures of from'about 9 to about 150 C. and occursspontaneously or may be catalyzed by a basic catalyst, such as a smallamount of sodium carbonate, sodium acetate; sodium hydroxide, or otheralcali metal base or basicaeting salt, pyridine, qu'inoline, a trialkylammonium hydroxide, or a lithitun, sodium or potassium alcoholate, suchas sodium methanolate. The resulting reaction forms predominantly an.N-alkylarylcarbamic' acid ester of the alkanolamine, which, in the caseof utilizing monoethanolamine, one of the preferred alkanolamines ofthis invention, yields a producthaving the following structure:

It (n Par-mire -0 onnNm the product'containing an amino group bearing anactive hydrogen atom which enters into the subsequent condensationreaction with the alkylcne imine to form the polyalkylenepolyaminohydrophilic portion of the present surface active product.

The reactants referred toherein as the alkylene imines which uponcondensation with the urethane intermediate product (i. e. the reactionproduct of the alkylarylisocyanate and the .alkano'larnine) introducethe watersolubilizing polyalkylenepolyamino chain into the structure ofthe .i esultingcompound, are cyclic compounds corresponding to thegeneral formula:

wherein nt is .a whole number having a value of from 2 to or, morespecifically, to the formula:

Thus, monomeric alkylene imines such as ethylene imine.

propylene imine, and n-butylene imine, one or more of the isobutyleneimines, and one or more ofthe amulenc imine isomers may be utilizedindividually or in admitture in the final condensation reaction to form,the present products.

Instead of utilizing the alk'ylene imine monomer itself in the finalcondensation reaction to form the ultimate surface active product ofthis invention, the alkylene imines may be polymerized or condensedwithiammonia (i. e. inter-condensed) in a reaction preceding theircondensation with the isocyanate-alkanol amine intermediate product .totheir desired molecular weight to yield a p0lyalkylenepolyarnine whichis readily soluble in water and which whencondensed with the isocyanatealkanolamine intermediate condensation product introduces thehydrophilic group essential to the development of surface activ ity inthe resulting product. In the preferred process of effecting theintroduction of the polyalkylenepolyamino chain intothe structure ofthe-product, the alkyleneimine monomer is charged directly to thecondensation reaction 8 with the isocyanate-alkanolamine intermediatereaction product to form the present product. Thepolyalkylenepolyami'nes formed by inter-condensation of thealkyleneimineimon'omer may also be polymerized in a preliminary reaction in thepresence of ammonia to form a polyalkylenepolyamino chain containingterminal amino groups on both ends of the polyalkylenepolyamino chainwhich'may undergo condensation with the isocyanatealkanolaminet reactantin the formation of the present surface active :agent. I

The condensation of the alkylene imine or polyalkylenepolyamine withtheintermediate condensation product of the alkylary'l isocyanate and theallranolamine to introduce the. 'polyalkylenepolyaminc hydrophilicradical into the compound may be effected thermally ata reactiontemperature of from about 30 to about 290 C., preferably at temperaturesof from about 50 to about C. The condensation reaction maybe promoted bythe'presence of a catalyst selected from the mineral acids in thereaction mixture, the acid also forming the acid ammonium salt of theamino groups present in the product. The reaction rate and completion ofthe condensation reaction is also promoted by excluding moisture fromthe reaction mixture, such as the moisture in troduced by reagentscontaining small amounts of dissolved water. In many instances it isalso desirable to conduct the condensation reaction in the presence of asolvent of one or more of the reactants, the solvent being generallyselected from certain hydrocarbons, preferably aromatic hydrocarbons,such as benzene, toluene, etc., chlorohydrocarbons, such aschlorobenzene, etc., and others such as diethyl ethers, dibutyl ether,etc., particularly solvents having boiling points corresponding to thedesired reaction temperature. The condensation of the alkylene imine andthe isocyanate-alkanolamine intermediate may also be conducted at asuperatmospheric pressure sufiicient to maintain the reactants and/orsolvent in substantially liquid phase during the course of the reaction, pressures up to about 30 atmospheres generally being sufiicientfor this purpose.

In the condensation of .the alkylene imine reactant with theintermediate urethane-type compound formed by the intermediatecondensation of the alkylaryl isocyanate with the amino alkanol, thesurface active product has the following general structure:

wherein C I-I represents the alkylene group of the alkanol aminereactant involved in the formation of the intermediate, urethanecontaining from 2 to 5 carbon atoms, b+c represents the number ofalkanol groups in the alkanol amine reactant, being from 1 to 3, and Rrepresents the alkylene group of the alkylene imine orpolyalkylenepolyamine reactant. The molar proportion of alkylene imineor polyalkylenepolyamine to the allay!- arylisocyanate condensationproduct of the alkanolaminc charged to the condensation reaction issufficient to form a polyalkylenepolyarnine chain having hydrophilicprop erties and for this purpose, at least 5 moles of the alkylene iminemonomer or an alkylene imine polymer contaim'ng at least 5 alkyleneaminounits per molecule must be charged into the reaction mixture with thealkylarylisocyanate-alkanolamine condensation product. Products havingdetergent properties generally contain at least 10 and preferably from15 to 25 alkyleneamino units per molecule and in order to provide apolyalkylenepolyamino chain of such length, a corresponding quantity ofalkylene imine or apolyalkylenepolyamine of such chain length must beprovided in the final condensation reaction. The latter reaction is alsopromoted by the presence of a mineral acid catalyst in the reactionmixture which forms the tetravalent ammonium salt of the amino groupspresent in the compound. The condensation of estates these reactantsalso occurs at the reaction conditions heree 30 to about 200 C.

The surface active products of this invention vary in their generalphysical properties, particularly their physical form and meltingpoints, depending upon the reactants involved in the condensationreaction and more particularly, upon the molecular weight of thealkylarylisocyanate reactant (i. e. the chain length of the alkylsubstituent thereof) and also upon the chain length of thepolyalkylenepolyamino radical, the latter factor being determined by thenumber of mols of alkylene imine condensed with theisocyanate-alkanolamine intermediate product or upon the number ofalkyleneamino units in the polyalkylenepolyamine reactant, if utilizedin the final condensation reaction. In the case of the low molecularweight alkylene imines, such as ethylene imine and the condensationproducts containing relatively few alkylene amino units in thehydrophilic chain, generally up to about 15, the product may be aviscous liquid which is only partly soluble in water but soluble inorganic solvents such as hydrocarbons, esters and alcohols. As thenumber of alkylene amino units in the polyalhylenepolyamino chainincreases, by increasing the number of mole of alkylene imine chargedinto the condensation reaction, the products become more soluble inwater and are of higher melting points. These products generally acquirewax-like or soap-like characteristics as thenumber of alkyleneaminounits per molecule increases. The latter materials form stable colloidswhen dissolved in water, and have many of the desirable physicalproperties of fatty acid soaps, such as the characteristic mucilaginousquality of soap solutions.

The present products, which form non-ionic or slightly cationic micellesin aqueous solution, are compatible in admixture with cationic, anionicand other non-ionic detergents. They may be composited with other" typesof detergents either in liquid or solid form and are thus particularlydesirable for the manufacture of neutral or slightly alkaline,non-irritatingdetergents in bar form, either individually or inadmixture with an anionic, ca-

tionic or other non-ionic, substantially neutral, organic detergent. Ingeneral, the composition preferably contains a major proportion of thepresent detergents in order to impart the desired soap-like feel to thecomposition. Builder salts, such as sodium sulfate, sodiumpolyphosphate, sodium silicate, and others well-known in the art, aswell as extenders, abrasives, perfumes, Watersoftening compounds,soil-suspending agents, .and other materials having a specific action indetergent use may be composited with the present products to enhancetheir detergent and cleansing properties ortheir customer appeal.

In some instances it becomes desirable for certain purposes to convert aWater-insoluble product to a watersoluble product. and in such instancesany free amino groups or hydroxyl groups which did not enter into thecondensation reaction with the isocyanate reactant may be converted toderivative salts or esters to promote the water-solubility of theresultant condensation. Thus, a free amino group may be converted to thecorresponding ammonium chloride or ammonium sulfate salt which is moresoluble in water than the original amino-substituted product. Althoughmineral acids, .in general, such as sulfuric acid, hydrochloric acid,phosphoric 'acid', etc. are preferred for converting at least aportionof the amino groups to their ammonium derivative groups of the acidanion utilized, other acids, including the lower fatty acids, such asacetic acid may also be utilized for this purpose. In a similar manner,the product. containing free bydroxyl groups may be converted into morewater-soluble derivatives by reaction with sulfuric acid to form asulfate ester whichmay be used "as such in an aqueous system orconverted to an alkali metalrsalt .thereofto form a substantiallyneutral anionic detergent product Likewise, -a water-soluble product maybe converted. to a water-insoluble material by converting the free aminoand/ or hydroxyl groups of the product to the corresponding ester oramide. organic acids. p The present invention is further illustratedwith respect to specific embodiments thereof in the following examples.In thus providing specific illustrations of the invention it is :notthereby intended to limit the generally broad scope of the invention instrict accordance therewith.

EXAMPLE I.PRODUCTION OF ALKYLARYL HY- DROCARBQN STARTING MATERIAL Aseries of alkyltoluene and alkylnaphthalene hydrocarbons was prepared toprovide the initial starting 'ma-' terial in the production of thepresent alkylaryl iso'cyanate intermediates from which various surfaceactive products were prepared by the procedure hereinafter described.Alkyltoluene hydrocarbons in which the alkyl groups are hexyl, nonylanddodecyl and'alkylnaphthalenes in which the alkyl groups are amyl andoctyl were prepared by alkylating toluene in the presence of an acidiccondensation catalyst with olefinic alkylating agents comprisingpropylene polymer fractions containing, respectively, a predominantproportion of hexylene, nonylene and dodecylene as the correspondingalkylating agents for toluene and n-amyle'ne and n-octylene (prepared bydehydrating n-amyl alcohol and n-octanol, respectively) for naphthalene.The following procedure describes the method of preparing nonyltoluene,the pro cedure, reaction conditions, molar ratios, alkylation catalystand other factors for the alkylation'reaction being substantiallysimilar in all respects for the alkylation of naphthalene with amyleneand octylene and for the alkylation of toluene with hexylene anddodecylene as for the herein described alkylation of toluene withnonylene, The boiling points and analyses of the alkylates for each ofsaid hydrocarbonalkylates varied in accordance with 7 their molecularWeights.

Preparation of nonyltoluene acid was charged to the other droppingfunnel and the v two materials thereafter simultaneouslyintroduced intothe alkylating fiask where the mixture was. efliciently stirred ata'temperature of, approximately 5 C. over a period of 3 hours. Uponsettling, the reaction mixture separated into two layers 'andthe loweracid. layer was decanted and discarded. The" upper hydrocarbonlayer waswashed with water and sodium bicarbonate, dried and subjected tofractional distillation. The fraction having a boiling range of fromabout 270 to about 280 C. was separated as the nonyltoluene product, thefraction having the indicated boiling range Weighing 846.grams. Analysisof the above alkylate fraction for carbon and hydrogen indicated thatthe product separated from the reaction mixture as indicatedcorresponded to the theoretical analysis for nonyltoluene, c eHgg,within the limits of experimental error. Y

Preparation of alkylaryliso'cyamzte. derivatives of alkylarylhydrocarbons e A. Mon o nitronohyltoluene. In the case of each of Q theabove'toluene'and naphthalene alkylates, that is, the

hexyltoluene, nonyltoluene, dodecyltoluene, amylnaphthalene, andoctylnaph thalene,- the isocyanate. derivatives thereof were prepared{in accordance with a uniform derivatives of appropriately selectedprocedure tor each alkylate, the procedure involving initially nitratingthe allrylatehydrocarbon to ;p1;oduce the mononitroasubstitutedintermediate, reducing the nitro. group of the product to form thecorresponding alkyltoluidines and alkylnaphthylamines, and reacting thelatter productswithphosgene (carbonyl chloride) to form thecorresponding isocyanate groups. Since a similar procedure was utilizedto prepare the isocyanate derivatives for each of the toluene andnaphthalene alkylates, the basic method involved will be described forthe preparation of nonyltolylisocyanate, the method being repeated as toits basic procedure for the. preparation of the other toluene andnaphthalene alkylates.

A mixture of 181 grams of concentrated nitric acid (specific gravity1.42) and 280 grams of 98.5% sulfuric acid, was cooled to C. and thenadded dropw e over a period of, three hours with efiicient stirring to327 grams (1.50.1'n0ls) o.f..uouyltoluene contained in a l-literreaction vessel placed in a cooling bath of a mixture of salt and ice,which controlled the reaction temperature during this period at.approximately 03 C. The cooling bath was then removed and the heat ofreaction raised the temperature to 50 C. where it was maintained anadditional two hours, accompanied by stirring;

After cooling, the organic layer was separated from the acid layer,diluted, with an equal. volume of pentane, washed with. water and sodiumbicarbonate and dried over calcium chloride. moved by distillation atatmospheric pressure and the remaining high-boiling material wasfractionally distilled at a pressure of 2-3 mm. Hg absolute. Thefraction boiling from. 143 to 148 C. at 2 mm. pressure, having .arefractive .index (12 of 1.5175, was separated; it weighed 302. grams.Analysis of this fraction for nitrogen and comparison of the result withthe thoretical nitrogen content for the pure compound resulted in thefollowing data: a

Nitrogen analysis.-Calculated for C H NO N, 5.32%. Found: N, 5.25%.

B. Nonylzoluidine.-The procedure employed for the reduction of the nitrogroup of mono-nitrononyltoluene was substantially similar to theprocedure employed for reduction of the nitro group of the correspondingmononitrohexyltoluene, mono-nitrododecyltoluene,mono-nitroamylnaphthalene, and mono-nitro-octylnaphthalene.derivatives.The reduction. of the nitro group only of the mono-nitrononyltoluenewithout reduction of the aryl nucleus thereof was efiected in accordancewith the following procedure: 300 grams (1.14 mols) of mono-nitro-'nonyltoluene, dissolved in 200 cc. of absolute ethanol, was charged withgrams .of a nickel-kieselguhr catalyst into a 3 li ter pressure;autoclave containing a glass liner, sealed, and; pressured to 100atmospheres ofhydrogen. The bomb was rotatedat 25 C. for 7 hours duringwhich time the pressure was maintained substantially constant. Followingthe above reduction period, the batch was removed, the catalyst filteredfrom the liquid product and the ethanol recovered by distillation atatmospheric pressure. The higher boiling bottoms material was fractionated at a pressure of about 2 3 mm. Hg absolute pressure. The recoveredvnonyltoluidine fraction boiling from 123 to 128 C. at 2 mm. Hg pressurewas collected'frorn the overhead distillate. Its refractive index (n P)was 1.5230, its-specific gravity was 0.9284 and the productyicld was96.5% of theoretical. The product had an observed molecular refractionof 76.7, compared to the theoretical value for nonyltoluidine of 76.8.Analysis of the product compared with the calculated nitrogen contentindicated the following results:

Nitrogen analysis.Calc ulated for CsHgqNl N, 6.01%. Found: N, 6.01%.

Preparation of a lkylaryl isocyanates V "I he following procedure forthe preparation of 'n o'nylitolylisocyanate from nonyltoluidine issubstantially the The pentane solvent was resame as that employed forthe preparation of the corresponding hexyland dodecyltolylisocyanatesand the arnyland octylnaphthalene isocyanates utilizing the re phosgcnc(carbonyl chloride) in the presence of an inert solvent, and thereafterfractionally distilling the product to separate the desiredalkylarylisocyanate product.

Nonyltolylisocyanate.Anl1ydrous ethyl acetate (3'75 mols) was placed ina 3-literflask and saturated with carbonyl chloride by bubbling thelatter into the solvent at room temperature. 7 A solution of grams(0.750 mol) of nonyltoluidine in 1125 cc. of ethyl acetate was addeddropwise to the saturated solution of phosgene ,in ethyl acetate over aperiod of five hours while an additional quantity of carbonyl chloridewas bubbled into the reaction mixture which was maintained in aturbulent state by eflicient stirring. The mixture was then heated bymeans of a steam bath and the bulk of the ethyl acetate was distilledoverhead 'at a slightly sub-atmospheric pressure. The remaining productwas distilled at 2 mm. Hg absolute pressure and fractions of the productwere collected. A fraction boiling from 122 to 126 .C. at 2 mm.pressure, amounting to 178.3 grams or a theoretical yield of 92%, wasseparated as the nonyltolylisocyanate product. The observed molecularrefraction for the product was 80.6, compared to a theoretical value of82.2; its indexiof refraction (11 was 1.5142, its specific gravity was0.9675 and its nitrogen analysis is indicated as follows:

Analysis-Calculated for C H NO: 5.40%. Found: 5.57%.

Condensation of alkylaryllisocyaizate with amino-substitutedwater-solubilizing organic compounds A. Condensation ofdodecylzolylisocyanate. with ethanol amine.6.l grams ofmono-ethanolamine (0.1 mole) was dissolved in 25 cc. of chloroform anddried-over-an' hydrous calcium sulfate.

the chloroform from the mixture and vacuum distillation (at 2 mm. Hgpressure) of the residue. Small amounts of unreacted ethanolamine wereremoved from the reaction mixture by dissolving the latterin chloroformand extracting the ethanolamine from the solution in three aliquots ofwater. The extracted chloroform solution of the product was dried overanhydrous calcium sulfate and the desired product recovered byevaporation of the chloroform from the dried solution. The product,residue of the evaporation, was a yellow liquid only'very slightlysoluble in warm water." It is believed to be princ'ipally' a mixture oftwo or more compounds (A and B), of the following structures in which (RRAr-) is dodecyltolyl, although compound (A) is believed to be thepredominant producte Small amountjslof the products resulting fromcondensation of two mols of isocyanate with one of ethanolamine Thedried solution was then placed in a reaction vessel and mixed withdodecyltolyl;

The reaction was allowed to continue may also have been present.Theabove product has no detersive activity and is insoluble in water,having no- A water-soluble, surface active product,'h aving deter--gency in aqueous solution was prepared from the above product or mixtureof compounds by reaction with ethyl ene imine. For this purpose, aliquotsamples of a larger batch of the product were each reacted with varyingproportions of ethylene imine to yield products containing an average of3,. 8, 10, 18 and 36 ethylene imine units per molecule. A mixture of 0.1mole of the ethanoh amine-dodecyltolylisocyanate condensation product,(molecular weight based upon Formula A, above), 10 grams of sodiumcarbonate and 0.3, 0.8, 1.0, 1.8 and 3.6 moles of ethylene imine,respectively, were charged into the glass liner of a rotating autoclavein successive runs and each heated to 50 C. at'the existing pressure inthe autoclave for 3 hours while the reaction mixture was stirred byrotation of the autoclave. The reaction products in each case wereremoved from the autoclave and tested for water solubility anddetergency. The products varied from viscous liquids (product containing3 ethyleneamino units per molecule) to pasty solids.(.product containing8 and 10 units of ethylene imine) to solid wax-like materials in thecase of the products containing an average of 18 and 36 units. ofethylene imine. Each product had surface activity as evidenced by thedepression of the surface tension of. water in which each was at leastpartially soluble, the product containing an average of 18 ethyleneimine. units having the greatest detergency. The products containing 8,10, lS'and 36 ethylene imine units were completely soluble in both hotand cold water at all concentrations below by weight. The detergency ofthe product containing 18 ethyleneamino units as measured by comparisonwith equivalent concentrations of sodium dodecylbenzene sulfonate in astandard Launder-O-Meter procedure under equivalent test conditions isapproximately 150% the detergency of the above indicatedreferencedetergent at concentrations of 0.2% ofeach detergent in aqueoussolution.

In a similar series of experiments in which phenylisocyanate andhexyltolylisocyanate were condensed with ethanolamine and the resultingintermediate products condensed with molar proportions of ethyleneimine, the product prepared from phenylisocyanate has only slightdodecyltolyl radical, althou (A) predominates in the product.

The intermediate product of the above reaction comprising the residuerecovered by evaporation of the chloro form solvent therefrom isconverted into a water-soluble surface active agent by reaction oftheintermediate with propylene imine utilizing sufficient imine inthereaction mixture to form a hydrophilic polypropylene polyamine chain.For this purpose, the dodecyltolylisocyanate condensation product ofdiethanolamine, prepared as indicated above is charged, together with 24molecular proportions of propylene imine and 1 percent of powderedsodium hydroxide catalyst into a rotating pressure autoclave, 21 grams(0.05 mole based upon Formula A, above) of the'intermediate product and69.5 *grams'of the propylene imine'b'e'ing utilized in the reaction. Theautoclave was thereafter heated for six hours at 90 C. as the autoclavewas rotatedto mix the reactants. Dur- 7 ing the ensuing reaction, thetemperature temporarily insurface activity and no apparent detersiveactivity, while the product prepared from hexyltolyl isocyanate,although exhibiting considerable surface activity was only slightlyeffective as an aqueous detergent.

B. Condensation of dodecyltolylisocyanate with di ezhanolamine andpropylene imine.--10.5 grams of diethanolamine (0.1 mol) was dissolvedin 25 cc. of chloroform and dried over calcium sulfate. The driedsolution was then placed in a reaction vessel and mixed withdodecyltolylisocyanate (15.1 grams-0.05 mole) added dropwise at roomtemperature, accompanied by etficient stirring. As the isocyanatereactant was added to the solution, the latter became spontaneously warmfrom the resulting reaction. The reaction mixture was stirred anadditional two hours and the solvent was thereafter removed bydistillation on a water bath and subsequent distillation at 2 mm. Hgabsolute pressure. Unreacted di' ethanolamine was removed by dissolvingthe product in 100 cc. of chloroform and extracting the resultingsolution three times with 20 cc. portions of water. The resicreased toabout 135 C. as the result of theexothermic reaction. Following theabove'period of reaction, the

' reaction product was heated to 120 C. and the molten product decantedfrom the residue of catalyst. 0n cools ing slightly, the productsolidified to a solid, wax-like material which produced a profusion oflather when shaken with water, and had excellent emulsifying properties.When tested for its detergent properties, the product has'a detersiveaction in aqueous solution greater than sodium dodecylbenzene sulfonateat equivalent concentrations and under equivalent test conditions.

C. Condensation of dodecylisocyanate with tl iethanolamine and ethyleneimine.l49 grams of triethanolamine (0.1 mole) was dissolved in St) cc-.of chloroform and therresu'lting solution dried over anhydrous calciumsulfate. The dried'solution was then placed in a reaction vessel andmixed with 30.1 grams (0.1 mole)'of dodecyl tolylisocyanate dissolved in100cc. of chloroform; added dropwise 'at room temperature,.accompaniedby stirring f of the reaction mixture. The temperature of the re actionmixture increased spontaneously as the isocyanate was added to thetriethanolamine and following the com:

plete addition of isocyanate (after 3.5 hours) the mixture was stirredan additional 2 hours.

ethanolamine was removed from the reaction product by extraction of thechloroform solution with 20 CCrPGI' tions of water. The chloroformsolvent was removed from the reaction product by successivedistillations at atmoo. pherlc pressure, followed by vacuum distillationat 2 mm. Q

Hg absolute pressure. The residue, a highly viscous oily productweighing approximately '36 grams was insoluble 1n water toanyappreciable extent. The above intermedi ate product'is believed toconsist almost exclusivelyof due, consisting of 21 grams of slightlyyellow liquid,

was insoluble in water. The product was also insoluble in dilutehydrochloric acid. 7

Some of the structural configurations for the possible individualcomponents present in the product include compounds having the followingempirical formulas (A,

B, C, D) in which R' RArrepresents the hydrophobic compounds (A and B)of the following structure, in which R'RArindicates a dodecyltolylradical, although compound (B) is believed to represent the structure ofa major proportion of the producti The intermediateisocyanate-triethanolamine condensahit is believed that co po ndUnreacted dition product prepared as indicated above is converted to Vf5 a a water-soluble product possessing detergent activity in aqueoussolution by reacting the intermediate product with 30 molar proportionsof ethylene imine in the presence of 1.0% of the reaction mixture ofsodium methylate.

The above intermediate product is placed in the glass liner of arotating pressure autoclave together with 1,.6 grams of sodium methylateand 132 grams, (3.0V moles) of ethylene imine liquefied in the glassliner by cooling the latter to C. A spontaneous reaction occurs when thereactants are mixed and is completed by heating the reaction mixture to150 C., accompanied by rotating the autoclave. The product solidifies toa waxy solid on cooling to 85 C. and is soluble in water at allconcentrations tested below by weight. The product has a detergency inaqueous solution about equal to sodium dodecylbenzeue sulfonate atequivalent aqueous concentrations and under otherwise equivalentdetergency testing conditions.

Products similar to the above alkylcne imine condensat'ion products ofdodecyltolyl'isocyanate with mono-, 'diand triethanolamina varying onlyslightly in detergency therefrom, may be prepared from the correspondingdodecyltolylisocyanate-mono-, di-, and tripropanolamine intermediates.The amylnaphthalene and octylnaphthalene isocyanate derivatives yieldmono-, di-, and triethanolamine condensation products having similarproperties to the dodecyltolylisocyanate mono-, di-, and triethanolamineintermediates, except that the naphthalene derivatives have highermelting points ,and when condensed with ethylene imine to yield productscontaining up to 40alkyleneamino units per molecule, form productspossessing surface activity, but of substantially lesser detersiveactivity in aqueoussolution. The latter products are of lessersolubility in water, but dissolve to a greater extent in non-aqueoussolvents such as aromatic hydrocarbons, ethylacetate,,etc.

1% We claim as our invention: A detergent having the following formula:

' 3-(u+b+a) [x].- N.[(R1NH).H]' (HZ):

(R1O) (R1NH)IH]$ in which X is a urethano group having the structurecorresponding to 1 the formula:

wherein Ar is a poly-substituted benzene hydrocarbon group, R isan alkylgroup containing from 8 to about carbon BIOIIISLR' is an alkyl groupcontaining from 1 to 2 carbon atoms, n is a whole number selected fromI), l and 2, R and R are independentlyselected from divalent alkylengroups containing from 2 to 3 carbon atoms, a is selected'frorn land 2,b and c are selected from 0, 1, and 2,'b-{-c being at least 1, a-I-b-l-cbeing a whole number less than 4, Z is an acid-derived anion, t isselected from 0, ,1 and a whole number having a value from 1 to1+s(b'+c)ands is a whole number selected from 5 to about 150, furthercharacterized in that the total number of (R NH) units in said detergentis not greater than about 150.

References Cited in the file of this patent ED STATES PATENTS 2,103,872Schoeller et al Dec. 28, 1937 FOREIGN PATENTS 470,181 Great Britain l.Aug. 3, 1937 536,686 Great Britain Nov. 21, 1940 7 OTHER REFERENCESTallis: Chem. Abs. 36, 1790 (1942).

